2,6,-dinitra-4-trifluoromethyl-anilines

ABSTRACT

New and valuable substituted dinitroanilines and a process for controlling the growth of unwanted plants with these compounds.

United States Patent Kiehs et a]. [451 Aug. 1, 1972 [54]2,6-DINITRA-4-TRIFLUOROMETHYL- ANILINES [56] References Cited [72]Inventors: Karl Kiehs; Karl-Heinz Koenlg, UNITED STATES PATENTS both ofLudwigshafen; Adolf h M t t, 2,792,296 5/1957 Hemmger ..260/465 E 'f'Germany 3,237,100 11/1966 11611161 211 ..260/465 E Asslgneei Badische n-& s a k- 1,915,334 6/1933 Salzberg et a1 ..260/243 tiengesellschaft,Ludwigshafen 3,227,734 1/1966 Soloway etal ..260/397.6 L Y 3,257,1906/1966 Soper ..260/577 3,442,639 5/1969 Soper ..260/577 [22] 19683,466,329 9/1969 Soper ..260/577 [21] Appl. No.: 784,247

Primary Examiner-Henry R. Jiles Assistant ExaminerS. D. Winters [3O]Fore'gn Application Priority Dam Attorney-Marla", Johnston, Cook & RootDec. 21, 1967 Germany ..P 16 43 719.7

[57] ABSTRACT [52] "260/465 E260/577 0 2 New and valuable substituteddinitroanilines and a recess for controllin the rowth of unwanted lants51 1111.01 ..C07c 121/52 fvith these compound: 3 p [58] Field of Search..260/397.6, 465 E, 573, 577,

260/2 39 B 1 Claim, No Drawings 2,6,-DINITRA-4-TRIFLUOROMETl-lYL-Am Thepresent invention relates to new and valuable substituteddinitroanilines and a process for controlling the growth of unwantedplants with these compounds.

it is known to use N,N-dipropyl-4-trifluoromethyl- 2,6-dinitroanilinefor controlling the growth of unwanted plants, especially in cotton.

An object of the invention is new and valuable substituteddinitroanilines. More particularly an object of the invention is new andvaluable 2,6-dinitroanilines. Yet another object of the invention isaprocess for controlling the growth of unwanted :plants without damagingcrop plants.

These and other objects of the invention are achieved by substituteddinitroanilines having the formula in which one of the radicals Rdenotes a nitro group and the R denotes a, trifluoromethyl radical, Rand R are identical or different and each denotes a lower alkyl radicalbearing, preferably tenninally, at least one halogen, cyano, hydroxy oralltoxy radical as a substituent, one of the radicals R and R may alsobe an alkenyl radical when the other of these radicals is a lower alkylradical bearing substituents as stated above. These substituteddinitroanilines have good herbicidal action and, when compared withactive ingredients of similar constitution, have superior plantcompatibility.

The new compounds may be applied as herbicides as solutions, emulsions,suspensions or dusts. The form of application depends entirely on thepurpose for which the agents are being used; in any case it shouldensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct mineral oilfractions with medium to high boiling points, such as kerosine or dieseloil, coal tar oils and oils of vegetable or animal origin, cyclichydrocarbons, such as tetrahydronaphthalene, and alkylated naphthalenesare suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastesor wettable powders by adding water. To prepare emulsions theingredients as such or dissolved in a solvent may be homogenized inwater by means of wetting or dispersing agents, eg a polyethylene oxideadduct. Concentrates which are suitable for dilution with water may beprepared from active ingredient, emulsifying or dispersing agent andpossibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients witha solid carrier, e.g. diatomaceous earth or fertilizers.

The new compound may be prepared for example by reaction of substituteddinitrochlorobenzenes with substituted amines. They are crystalline ornon-distillable oils.

The following examples illustrate the preparation of specific compoundsaccording to this invention.

EXAMPLEI brownoil (93 percent ofthe theory).

Analysis:

c H N calm: 43.0 3.6 12.5 rm: 43.2 3.6 12.0

EXAMPLE 2 Preparation of N-chloroethyl-N-allyl-2,6-dinitro-4-trifluoromethylaniline 16.7 parts by weight ofN-hydroxyethyl-N-allyl-2,6- dinitro-4-trifluoromethylaniline isdissolved in 50 parts by weight of benzene. After adding 1 part byweight of dimethylformamide and dripping in 30 parts by weight ofthionyl chloride at room temperature the whole is boiled for 2 hoursunder reflux. The volatile constituents are distilled ofl' from thereaction mixture at 20 mmHg, the residue is taken up in ethyl acetate,the solution is washed with ice-water, then with 10 percent sodiumbicarbonate solution and finally again with water and the organic phaseis dried over sodium sulfate.

After distilling 0B the solvent a dark brown oil percent of the theory)is obtained from which, after purifying over silica gel (benzene),yellow crystals may be isolated which have a melting point of 39 to 4 lC.

Analysis:

C H N Cl cakL: 40.7 3.l l L9 l0.0 found: 40.4 3.2 .6 9.9

Examples of substances prepared in the same way are:

N-chloroethyl-N-cyanoethyl4-trifluormethyl-2,6- dinitroaniline m.p. 66to 67 C N,N-bis-chloroethyl-2,-dinitro-p-toluidine m.p. 66 to 67 CN-propyl-N-cyanoethyl-2,4-dinitro-6- trifluoromethylaniline m.p. 56 CN-allyl-N-cyanomethyl-2,4-dinitro-6- trifluoromethylaniline m.p. 56 CN-methoxyethyl-N-cyanoethyl-4 trifluoromethyl- 2,6-dinitroaniline m.p.67 to 68 C N-n-butyl-N-cyanoethyl-4-trifluoromethyl-2,6- dinitroanilinem.p. 93 C.

The following comparative experiment demonstrates the superiority of thecompositions according to this invention over known active ingredients.

EXAMPLE 3 In a greenhouse, loamy sandy soil is filled into pots and thensown with the seeds of cotton (Gossypium sp.), Indian corn (Zea mays).soya beans (Glycine hispida), annual meadow grass (Poa annua), orchardgrass (Dactylis glomerata), slender foxtail (Alopecurus myosuroides) andbarnyard grass (Panicum crus-galli). The soil prepared in this manner istreated with 3 kg per hectare ofN-allyl-N-fi-chloroethylltrifluoromethyl-2,6-dinitroaniline (I), with 3kg per hectare of N-propyl-N-propargyl-4-(methylsulfonyl)-2,6-dinitroaniline (ll) and, for comparison, with 3 kg per hectare ofN,N-dipropyl-l-trifluoromethyl-Zfidinitroaniline (III), these amounts ofthe active ingredients each being dispersed in 500 liters of water perhectare. After 4 weeks it is ascertained that compounds I and II, whilehaving the same good herbicidal action as compound III, have superiorcompatibility with Indian com and soya beans.

The results of the experiment may be seen from the following table:

Active ingredient I [I ll! Crop plants: cotton -10 0-l0 0-10 Indian corn-20 10 30-40 soya beans to 0-10 30 Unwanted plants: annual meadow grass100 80-90 100 orchard grass )0 80-90 lOO slender foxtail 90- l 00 80-9090-] 00 barnyard grass 90-l00 80 90-l00 0 no damage I00 totaldestruction The following substances exhibit the same biological actionas l and ll:

N-methyl-N-chloroethyl-4-trifluoromethyl-2,6- dinitroanilineN,N-bis-chloroethyl-4-trifluoromethyl-2,6- dinitroanilineN-chloroethy]-N-cyanoethyl-4-trifluoromethyl-2,6- dinitroaniline 4N-chlonoethyl-N-( 'y-chloropropyl )4- trifluoromethyl-2,6-dinitroaniline N-propyl-N-cyanoethylt-trifluoromethyl-Z,6-dinitroaniline N-allyl-N-cyanoethyl-4-trifluoromethyl-2,6-dinitroaniline N-eflayl-N-cyanoethyl-4-trifluoromethyI-L6-dinitroaniline N,N-bis-cyanoethyl-4-trifluoromethyl-2,6- dinitroanilineN-propyl-N-cyanomethyl-4-trifluoromethyl-2,6- dinitroaniline N-allyl-N-cyanomethyl-4-trifl uoromethyl -2,6- dinitroanilineN-methoxyethyl-N-cyanomethyl-i-trifluoromethyl- 2,6-dinitroanilineN-propyl-N-chloroethyl-ZA-dinitro-fitrifl uoromethylanilineN,N-bis-chloroethyl-2,4-dinitro-6- trifluoromethylanilineN-propyl-N-cyanoethyl-2,4-dinitro-6- 1-'fi l'-i$n flf |-2,4-diniwe trifluoromethylaniline N-propyl-N-cyanomethyl-2,4-dinitro-6-trifluoromethylaniline N-propyl-N-B-chloroethyl-4-trifluoromethyl-2,6-dinitroaniline N-isopropyl-N-(y-chloropropyl)-4-trifluoromethyl-2,6-dinitroaniline We claim: 1. A compound having the formula wherein Rdenotes lower cyanoalk yl and R denotes ally], cyanoethyl, chloroethyl,ethyl, propyl. butyl or methoxyethyl.

* i i i

